CN106947082B - Pyrene thiazole benzothiazolyl organic porous polymer and preparation method thereof - Google Patents
Pyrene thiazole benzothiazolyl organic porous polymer and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
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Abstract
The present invention provides a kind of organic framework materials; under conditions of amine initiator and catalyst; by 1; 3; 6; (to the Fonnylphenyl) pyrene of 8- tetra- and two thioacetamides carry out polymerization reaction in organic solvent, obtain organic framework material, and the organic framework material has following structure unit:Organic framework material provided by the invention is the macromolecular network cross linked polymers comprising pyrene ring and thiazole and thiazole ring, is covalent organic framework material, stable structure.
Description
Technical field
The present invention relates to organic material technical fields more particularly to a kind of organic framework material and preparation method thereof.
Background technique
Porous organic framework materials have interconnected reticulated porous structures, therefore have relative to other materials than table
Area is big and the smaller advantage of density, is widely used in heterogeneous catalysis, hydrogen storage, absorption, ion exchange, gas
The fields such as separation.As porous organic framework materials have been to be concerned by more and more people, good material property attracts more
People go to probe into.
Porous organic framework materials divide metal-organic framework (MOFs) and covalent organic framework (COFs).The organic bone of metal-
Frame (MOFs) is also known as Hybrid compounds or coordination polymer, it is to utilize metal-coordination between organic ligand and metal ion
Complexing passes through the material with supermolecule porous network structure being self-assembly of.Due to organic ligand wide variety, gold
Belong to ion selection multiplicity, so that synthesis MOFs material has very big diversity, flexibility.Further, it is also possible to special by synthesis
Different organic ligand and specific metal ion are assembled to form the organic backbone of Focus.
However, some disadvantages of MOFs material lead to it, there are limitations in application: (1) losing solvent molecule in MOFs
Its structure starts to become unstable later, is easy to collapse containing bone porous structure, and aperture is caused to reduce or formed without fixed
The non-porous structure of shape；(2) environmentally sensitive: it is most of extremely sensitive to the hydrone in gas in MOFs material, it contacts long
It may result in the collapsing of the variation setting skeleton of structure；(3) structural characterization is relatively difficult；(4) adjustable pore diameter range
Small: the material in mesoporous region is higher to organic ligand structural strength requirements, but the increase with body length is along with dissolution properties
It is deteriorated.
Since the problem of MOFs material is exposed makes the development of the direction receive obstruction, technical staff is present
Research emphasis has been placed on covalent organic framework (COFs).However, the type of covalent organic framework material is very in the prior art
It is few, greatly limit the development of covalent organic framework.
Summary of the invention
It is provided by the invention new organic the purpose of the present invention is to provide a kind of organic framework material and preparation method thereof
Framework material has expanded the range of organic backbone.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of organic framework material, include the following steps:
1,3,6,8- tetra- (to Fonnylphenyl) pyrene and two thioacetamides are performed under heating conditions polymerization reaction, obtain
Organic framework material；
The organic framework material has following repetitive unit:
Preferably, the heating temperature of the polymerization reaction is 120-200 DEG C.
Preferably, the heating temperature of the polymerization reaction is 140-180 DEG C.
Preferably, the polymerization reaction carries out in the presence of a kind of organic solvent.
Preferably, the organic solvent includes n,N-Dimethylformamide, at least one of nitromethane or phenol.
Preferably, the polymerization reaction carries out under a kind of inert atmosphere.
Preferably, the inert atmosphere is nitrogen atmosphere.
The present invention also provides the organic framework materials that preparation method described in a kind of above-mentioned technical proposal obtains, to contain pyrene
The macromolecular network cross linked polymers of ring and thiazole and thiazole ring.
Detailed description of the invention
Fig. 1 is the infrared spectrum for the 1,3,6,8- tetrabromo pyrene that the present invention obtains；
Fig. 2 is the infrared spectrum of 1,3,6,8- tetra- (to Fonnylphenyl) pyrene that the present invention obtains；
Fig. 3 is the infrared spectrum for the organic framework material that the present invention obtains；
Fig. 4 is the thermogravimetric curve of organic framework material；
The SEM figure that Fig. 5 is the 10.0k of organic framework material；
The SEM figure that Fig. 6 is the 5.0k of organic framework material.
Specific embodiment
The present invention provides a kind of preparation methods of organic framework material, include the following steps:
1,3,6,8- tetra- (to Fonnylphenyl) pyrene and two thioacetamides are performed under heating conditions polymerization reaction, obtain
Organic framework material；
The organic framework material has following repetitive unit:
The present invention does not have special limit to the source of tetra- (to the Fonnylphenyl) pyrene of 1,3,6,8- and two thioacetamides
System using commercially available reagent as reactant, or according to synthetic method on document prepares reactant.
In the present invention, 1,3,6,8- tetra- (to Fonnylphenyl) pyrenes and two thioacetamides can be in a kind of organic solvents
In the presence of react.The organic solvent is preferably one of N,N-dimethylformamide, nitromethane or phenol or several
Kind.In the present invention, solvent includes two kinds, three kinds or four kinds group timesharing when described, each substance for being included can be with any
Mass fraction exists.
In the present invention, the temperature of the polymerization reaction is preferably 120~200 DEG C, and more preferably 140~180 DEG C.
In the present invention, the polymerization reaction can carry out under a kind of inert atmosphere.Preferably, the inert atmosphere is
Nitrogen atmosphere.
In the present invention, described 1, the molar ratio of 3,6,8- tetra- (to Fonnylphenyl) pyrenes and two thioacetamides is preferably
(1.5~2.5): 1, more preferably (1.7~2.3): 1, further preferably (1.9~2.1): 1.
The present invention preferably post-processes polymerizate, obtains organic framework material.In the present invention, the post-processing
Comprising washing and drying.
In the present invention, organic solvent can be used in the washing.The organic solvent can be N, N- dimethyl formyl
One of amine (DMF) and tetrahydrofuran (THF) or mixture, can also using it is well-known to those skilled in the art other
Organic solvent.
The present invention can specifically be dried in vacuo, drying, room temperature are dried under infrared lamp the no particular/special requirement of the drying
Or heating furnace is dry.The present invention does not have particular/special requirement to the temperature and time of the drying, can make to wash used organic
Solvent volatilization is clean.
The present invention also provides a kind of organic framework materials, which is characterized in that the organic framework material has following knot
Structure unit:
Organic framework material provided by the invention and preparation method thereof is described in detail below with reference to embodiment, but
It is that they cannot be interpreted as limiting the scope of the present invention.
In some embodiments, organic solvent can be used.Organic solvent can be N,N-dimethylformamide (DMF),
One of nitromethane or phenol are a variety of.Organic solvent can also not used.In a heated condition, reactant can be with
It melts and forms mixture and carry out polymerization reaction.
Embodiment 1
It takes pyrene (5.0369g, 24mmol) to be placed in clean beaker with spoon, measures nitrobenzene (100mL) and pour into beaker
Middle stirring and dissolving starts that bromine (5.6mL, 109mmol) is slowly added dropwise with drop-wise until completely dissolved, then by reaction system
120 DEG C are warming up to, the reaction time is 14 hours, and reaction solution color is transformed into khaki, and the crude product being obtained by filtration is super with ethyl alcohol
Sound cleans 3 times, obtains 1,3,6,8- tetra- bromo pyrene of light green solid, yield 6.2687g.
Embodiment 2
Palladium chloride (0.0942g) is added in round-bottomed flask (250mL), triphenylphosphine (0.643g) and dimethyl sulfoxide
(7.5ml) solution, under the protection of nitrogen, until reaction system is heated to solid matter whole dissolution, entire solution is presented
Yellow, and it is transparent.Reaction temperature closes oil bath at 130 DEG C to 140 DEG C or so, after hydrazine hydrate (4 drop) is added, there is glassy yellow
Solid matter is precipitated, and quickly filters, is being washed respectively with ethyl alcohol (5ml*2) and dehydrated alcohol (5ml*2), is dried in vacuo
After obtain bright yellow solid 0.2675g, saved under nitrogen.
Embodiment 3
1,3,6,8- tetrabromo pyrenes (1.0039g) are mixed, 4- is to formyl phenylboronic acid (1.7540g), four catalyst of palladium
(0.2675g) and potassium carbonate (2.2044g) stir three days under a nitrogen and at 85 DEG C in dry tetrahydrofuran (30ml),
Then yellow suspension liquid mixture is poured into ice and is stirred, concentrated hydrochloric acid is contained in ice, then mixture is filtered, filtered
The 2M salt acid elution 3 times (20ml) of product afterwards, washed product continues to be extracted with chloroform (3*100ml), after taking lower layer's solution
After being dried, filtered with magnesium sulfate, the solid residue that solvent is obtained under reduced pressure recrystallizes in chloroform, obtains a kind of bright
Yellow product 1,3,6,8- tetra- (to Fonnylphenyl) pyrene (0.2355g).
Embodiment 4
(to the Fonnylphenyl) pyrene of 1,3,6,8- tetra- 0.1230g is added in the autoclave of teflon lined
(0.20mmol) and two thioacetamide 0.0480g (0.40mmol).3ml anhydrous DMF is added, inflated with nitrogen 5 minutes, is sealed
After good reaction kettle.It is placed in baking oven, temperature control is reacted 12 hours at 200 DEG C, is cooled to room temperature filtering, is washed 2 times with DMF
Unreacted substance is removed, after reaction, product passes through tetrahydrofuran Soxhlet extraction 24 hours, product kept dry.
Embodiment 5
(to the Fonnylphenyl) pyrene of 1,3,6,8- tetra- 0.1230g is added in the autoclave of teflon lined
(0.20mmol) and two thioacetamide 0.0480g (0.40mmol).The anhydrous nitromethane of 3ml, which is added, with DMF volume ratio is
The mixed solvent of 1:1, inflated with nitrogen 5 minutes, after reaction kettle is sealed.It is placed in baking oven, temperature control is small in 180 DEG C of reactions 12
When, it is cooled to room temperature filtering, 2 times is washed with DMF and removes unreacted substance, after reaction, product passes through tetrahydrofuran rope
Family name extracts 24 hours, product kept dry.
Embodiment 6
(to the Fonnylphenyl) pyrene of 1,3,6,8- tetra- 0.1230g is added in the autoclave of teflon lined
(0.20mmol) and two thioacetamide 0.0600g (0.50mmol).3ml anhydrous DMF is added, inflated with nitrogen 5 minutes, is sealed
After good reaction kettle.It is placed in baking oven, temperature control is reacted 24 hours at 160 DEG C, is cooled to room temperature filtering, is washed 2 times with DMF
Unreacted substance is removed, after reaction, product passes through tetrahydrofuran Soxhlet extraction 24 hours, product kept dry.
Embodiment 7
(to the Fonnylphenyl) pyrene of 1,3,6,8- tetra- 0.1230g is added in the autoclave of teflon lined
(0.20mmol) and two thioacetamide 0.0480g (0.40mmol).The anhydrous phenol of 3ml is added, inflated with nitrogen 5 minutes, is sealed
After good reaction kettle.It is placed in baking oven, temperature control is reacted 36 hours at 140 DEG C, is cooled to room temperature filtering, is washed 2 times with DMF
Unreacted substance is removed, after reaction, product passes through tetrahydrofuran Soxhlet extraction 24 hours, product kept dry.
Embodiment 8
(to the Fonnylphenyl) pyrene of 1,3,6,8- tetra- 0.1230g is added in the autoclave of teflon lined
(0.20mmol) and two thioacetamide 0.0480g (0.40mmol).Add the anhydrous nitromethane of 3ml, inflated with nitrogen 5 minutes,
After reaction kettle is sealed.It is placed in baking oven, temperature control is reacted 48 hours at 120 DEG C, filtering is cooled to room temperature, with anhydrous nitre
Methylmethane washs 2 times and removes unreacted substance, and after reaction, product passes through tetrahydrofuran Soxhlet extraction 24 hours, product
Kept dry.
Embodiment 9
(to the Fonnylphenyl) pyrene of 1,3,6,8- tetra- 0.1230g is added in the autoclave of teflon lined
(0.20mmol) and two thioacetamide 0.0480g (0.40mmol).Inflated with nitrogen 5 minutes, after reaction kettle is sealed.It is placed in baking
In case, temperature control is reacted 48 hours at 120 DEG C, is cooled to room temperature filtering, it is not anti-to wash 2 removings with anhydrous nitromethane
The substance answered, after reaction, product pass through tetrahydrofuran Soxhlet extraction 24 hours, product kept dry.
The polymerization reaction of aldehyde radical and two thioacetamides may follow following course:
By the reaction mechanism mechanism of reaction it is found that if containing multiple aldehyde radicals in precursors, chain or netted poly- may finally be generated
Close object.
Therefore 1,3,6,8- tetra- (to Fonnylphenyl) pyrene tool, is reacted there are four generally within the aldehyde radical in a plane
Product afterwards is also the network polymers of a hither plane.
Property and characterization
Infared spectrum analysis is carried out to 1,3,6,8- tetrabromo pyrene structure by Fig. 1, occurs main-C-Br's in Fig. 1
Characteristic peak (653.87cm-1), explanation-Br base have appeared on pyrene.- C-H (3100 on phenyl ring can be also seen that from map
~3000cm-1) and C=C double bond (1591.27cm-1) stretching vibration characteristic peak appearance.
Infrared spectrum analysis is carried out by structure of the Fig. 2 to 1,3,6,8-4 (4- Fonnylphenyl) pyrene.As shown in Fig. 2, knot
C=C (1600~1580cm-1), C-Br in phenyl ring (3100~3000cm-1), phenyl ring in conjunction 1,3,6,8- tetrabromo pyrene
The characteristic peak positions of (600-500cm-1) stretching vibration, it can be seen that phenyl ring in 1,3,6,8-4 (4- Fonnylphenyl) pyrene
The stretching vibration characteristic peak of C=C (1600.92cm-1) still has in (3043.67cm-1) and phenyl ring, and C=O aldehyde occurs
Base double-peak feature absorption peak (2723.49cm-1 and 2810.28cm-1) stretching vibration characteristic peak, meanwhile, C-Br stretching vibration
Characteristic peak appears in 513.07cm-1, but intensity is extremely weak, illustrates that Br is almost substituted.
By the infared spectrum of Fig. 3, and combine 1,3,6,8-4 (4- Fonnylphenyl) pyrene infared spectrums to XWB-COF-1
Structure analyzed, the C=O aldehyde radical double-peak feature absorption peak on 1,3,6,8-4 (4- Fonnylphenyl) pyrene
(2723.49cm-1And 2810.28cm-1) occur in the map it is unobvious, and on phenyl ring characteristic peak-C-H (3100~
3000cm-1) and C=C double bond (1604.77cm-1) stretching vibration peak still have, characteristic peak C-S is had also appeared in Fig. 3
(900~1300cm-1Between), peak value is weaker.
Fig. 4 is the thermal gravimetric analysis curve of organic framework material.As shown in Figure 4, A line is sample quality with temperature change
Curve, B line are curve of the hot-fluid with temperature change.After beginning to warm up heating, sample quality starts to reduce, this may be because
For sample dehydration.The evaporation rate of the water of sample surfaces absorption is relatively fast.When to about 60 DEG C, speed that sample quality reduces
Degree beginning is slack-off, illustrates that the evaporation of water at this time is slack-off.The water evaporation rate of sample interior is relatively slow.Sample between 60 to 400 DEG C
Quality variation is very slow, also illustrates that organic backbone is relatively stable.Organic backbone destroys after 400 DEG C.About 700
The weight of product starts to keep stablizing after DEG C, reaches 58%.Prove obtained organic framework material stable structure, thermostabilization
Performance is good.The variation of B line can also prove above-mentioned change procedure.
The SEM figure that Fig. 5 is the 10.0k for the organic framework material that the present invention obtains；Fig. 6 is the organic backbone that the present invention obtains
The SEM of the 5.0k of material schemes.Pass through electron microscopic picture, it can be seen that elongated club is presented in the organic framework material under Electronic Speculum
Shape, specific surface area with higher.
Claims (8)
1. a kind of preparation method of organic framework material, includes the following steps:
1,3,6,8- tetra- (to Fonnylphenyl) pyrene and two thioacetamides are performed under heating conditions polymerization reaction, had
Machine framework material；
The organic framework material has following repetitive unit:
2. preparation method according to claim 1, which is characterized in that the heating temperature of the polymerization reaction is 120-200
℃。
3. preparation method according to claim 2, which is characterized in that the heating temperature of the polymerization reaction is 140-180
℃。
4. preparation method according to claim 1 or 2, which is characterized in that presence of the polymerization reaction in organic solvent
Lower progress.
5. the preparation method according to claim 4, which is characterized in that the organic solvent includes N, N- dimethyl formyl
At least one of amine, nitromethane or phenol.
6. preparation method according to claim 1, which is characterized in that the polymerization reaction under a kind of inert atmosphere into
Row.
7. preparation method according to claim 6, which is characterized in that the inert atmosphere is nitrogen atmosphere.
8. a kind of organic framework material, which is characterized in that the organic framework material has the following structure unit:
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| CN107857881B (en) * | 2017-10-20 | 2020-09-11 | 兰州大学 | Benzoxazole-linked covalent organic framework material and synthesis method thereof |
| CN111484602B (en) * | 2019-01-28 | 2023-01-06 | 台州学院 | 1,3,6,8-tetra (p-formylphenyl) pyrene-based conjugated microporous polymer and preparation method thereof |
| CN110165124B (en) * | 2019-05-16 | 2022-02-22 | 华南师范大学 | Double-coating diaphragm applied to lithium-selenium disulfide battery and preparation method and application thereof |
| CN112574407B (en) * | 2019-09-27 | 2023-01-06 | 台州学院 | 2,4,6-tri (4-aldehyde phenyl) -1,3,5-triazine-based conjugated microporous polymer and preparation method thereof |
| CN111662450B (en) * | 2020-06-28 | 2021-07-27 | 山东大学 | Organic magnetic polymer material and preparation method thereof |
| CN112608490B (en) * | 2020-12-18 | 2022-04-12 | 华中科技大学 | Thioether-functionalized pyrenyl covalent organic framework material and preparation method and application thereof |
| CN114196018B (en) * | 2021-12-06 | 2023-04-11 | 福州大学 | Thiazolothiazolyl polymer and preparation method and application thereof |
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| EP2832767A1 (en) * | 2013-07-31 | 2015-02-04 | Fundación Imdea Nanociencia | Method for the Synthesis of Covalent Organic Frameworks |
| CN105885015A (en) * | 2014-12-26 | 2016-08-24 | 上海品益新材料科技有限公司 | Thiazole cross-linked porous organic polymer and preparation method thereof |
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| EP2832767A1 (en) * | 2013-07-31 | 2015-02-04 | Fundación Imdea Nanociencia | Method for the Synthesis of Covalent Organic Frameworks |
| CN105885015A (en) * | 2014-12-26 | 2016-08-24 | 上海品益新材料科技有限公司 | Thiazole cross-linked porous organic polymer and preparation method thereof |
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